Sven Hamann

Development of multifunctional thin films using high-throughput experimentation methods

Abstract This paper describes the use of thin film high-throughput experimentation methods for the efficient development of multifunctional materials, using Ni – Ti – X and ferromagnetic shape memory alloys as examples. The thin films were fabricated in the form of binary, ternary, and quaternary materials libraries by special magnetron sputter deposition processes. These materials libraries were subsequently processed and characterized by high-throughput experimentation methods in order to relate compositional information with structural and functional properties. For this, appropriate visualization of the data is necessary. Results show that the martensitically transforming regions in ternary thin films are generally larger than was known from literature. Within these regions, the variation of the functional properties can be mapped with respect to the composition and microstructure, and thus the most suitable materials for applications can be effectively selected.

Modular high-throughput test stand for versatile screening of thin-film materials libraries

Abstract Versatile high-throughput characterization tools are required for the development of new materials using combinatorial techniques. Here, we describe a modular, high-throughput test stand for the screening of thin-film materials libraries, which can carry out automated electrical, magnetic and magnetoresistance measurements in the temperature range of −40 to 300 °C. As a proof of concept, we measured the temperature-dependent resistance of Fe–Pd–Mn ferromagnetic shape-memory alloy materials libraries, revealing reversible martensitic transformations and the associated transformation temperatures. Magneto-optical screening measurements of a materials library identify ferromagnetic samples, whereas resistivity maps support the discovery of new phases. A distance sensor in the same setup allows stress measurements in materials libraries deposited on cantilever arrays. A combination of these methods offers a fast and reliable high-throughput characterization technology for searching for new materials. Using this approach, a composition region has been identified in the Fe–Pd–Mn system that combines ferromagnetism and martensitic transformation.

Correlation of phase transformations and magnetic properties in annealed epitaxial Fe–Pd magnetic shape memory alloy films

Single-crystal-like films are promising candidates for magnetic shape memory (MSM) applications on the microscale. For defect reduction and stress relaxation, we apply a heat treatment to pulsed laser deposited, partial epitaxial Fe–Pd films with different compositions. By recrystallization starting from the epitaxial interface, single-crystal-like films are obtained. Deformation twins being present in the as-deposited state are completely eliminated. The epitaxial (100) orientation allows clear monitoring of the transformation from face centered cubic (fcc) austenite to face centered tetragonal (fct) martensite by x-ray diffraction experiments. Transformation from fcc austenite to fct martensite is hindered by constraints from the substrate. At temperatures down to 125 K residual fcc austenite is present. Magnetic measurements performed down to 50 K indicate that during further cooling the phase transformation to body centered tetragonal martensite occurs. The results show that annealing of laser deposit...

Artificial Single Variant Martensite in Freestanding Fe70Pd30 Films Obtained by Coherent Epitaxial Growth

2010 WILEY-VCH Verlag Gmb Microactuators and sensors based on magnetic shape-memory (MSM) alloys will benefit from the large strain close to 10% obtained in these materials. These strains exceed the values obtainable by magnetostriction or piezoelectricity by more than one order of magnitude. Thus, they can be used directly for most applications, avoiding additional complications of mechanical amplification. As the highest strains to-date are obtained in bulk single crystals, the use of epitaxial films is most promising for microsystems, owing to their single-crystal-like microstructure. With reduced actuator size, however, the influence of interfaces, and in particular of oxidation, becomes more important. Though the prototype Ni2MnGa system is relatively inert, an oxide surface layer may hinder the martensitic transformation in thin films. For the Fe70Pd30 system [8] oxidation is expected not to be critical due to the high content of a noble element. In Fe70Pd30 the martensitic transformation occurs around room temperature (RT). First reports indicate that epitaxial growth of thin Fe70Pd30 films can be obtained already at RT. For epitaxial growth of the NiMnGa system, a minimum temperature of 350 8C is required. Recently it was shown that epitaxial growth of Fe70Pd30 is possible on various metallic buffers. Due to coherent growth, huge tetragonal distortions were stabilized in 50 nm thick films, covering most of the Bain transformation path from face-centered cubic (fcc) to bodycentered cubic (bcc) structure. Here, we show how this approach can be extended to obtain freestanding films of micrometer thickness, thus fulfilling both key requirements for the integration into microsystems as well as prerequisites for MSM films, that is, martensitic, ferromagnetic at RT, freestanding, and single-crystalline-like. In addition, our experiments reveal that the transformation behavior in these films differs from in the bulk. While this topic has been an extensive playground for theory, experiments are rare, since a detailed analysis often requires epitaxial films. Recently, experiments on epitaxial films, for example, have revealed a variant selection by the rigid interface to the substrate or by reduction of the magnetic stray field energy in freestanding films. The present experiments are more fundamental since they show that circumventing the forward martensitic transformation by forming the martensitic structure directly at RT hinders the nucleation of the reverse transformation to austenite. This remarkable suppression of the transformation not only gives a better understanding of the martensitic transformation but also opens innovative routes for microsensors. Films of Fe70Pd30, 1.2mm thick, were deposited with a low deposition rate of 0.024 nms 1 at 30W sputtering power in a magnetron sputtering system on Au-buffered MgO(001) oriented, epi-polished substrates. The crystal structure of the Fe70Pd30 films was analyzed by four-circle and temperature-dependent two-circle X-ray diffraction (XRD), where x and w denote the tilt and rotational angles, respectively. The u–2u scans (see Fig. 1a) show the 200 Au reflection of the buffer layer (2u1⁄4 44.448) as well as the Fe70Pd30 002 reflection (57.388). Assuming a constant volume of the Fe70Pd30 unit cell compared to the cubic austenite, [15] the lattice parameters a and c were calculated to be 0.287 nm and 0.321 nm ( 0.001 nm), respectively, which constitutes a c/a ratio of 1.12. Temperature-dependent XRD measurements showed no change in the crystal structure in the accessible temperature range between 150 and 375K. The pole figure of the 101 reflection reveals a four-fold symmetry (Fig. 1b). The maximum intensity is obtained at an average of 47.278 at w1⁄4 458. The peak in the w direction is rather sharp with a small full width at half maximum (FWHM), indicating well-oriented growth of the body-centered tetragonal (bct) unit cell rotated by 458compared to the edges of the MgO cell. The larger FWHM in the x direction indicates relaxation of the lattice. There are no indications that twinning has occurred in the film. The sample for transmission electron microscopy (TEM) investigations was prepared by focused ion beam (FIB) lift-out

Time- and space-resolved high-throughput characterization of stresses during sputtering and thermal processing of Al-Cr-N thin films

(Al100−xCrx)N thin-film materials libraries (x = 31–79 at%) were fabricated on micro-machined cantilever arrays, in order to simultaneously investigate the evolution of stresses during film growth as well as during thermal processing by analysing the changes in cantilever curvature. The issue of the dependence of stress in the growing films on composition, at comparable film thicknesses, was investigated. Among the various experimental parameters studied, it was found that the applied substrate bias has the strongest influence on stress evolution and microstructure formation. The compositions of the films, as well as the applied substrate bias, have a pronounced effect on the lattice parameter and the coherence length. For example, applying a substrate bias in general leads to compressive residual stress, increases the lattice parameter and decreases the coherence length. Moreover, bias can change the film texture from [1 1 1] orientation to [2 0 0]. Further detailed analysis using x-ray diffraction and transmission electron microscopy clearly revealed the presence of a [1 1 1] highly textured face centred cubic (B1 type) Al–Cr–N phase in the as-deposited state as well as the coexistence of the hexagonal [1 1 0] textured Cr2N phase, which forms in the Cr-rich region. These results show that the combinatorial approach provides insight into how stresses and compositions are related to phases and microstructures of different Al–Cr–N compositions fabricated in the form of materials libraries.

High-throughput characterization of stresses in thin film materials libraries using Si cantilever array wafers and digital holographic microscopy

We report the development of an advanced high-throughput stress characterization method for thin film materials libraries sputter-deposited on micro-machined cantilever arrays consisting of around 1500 cantilevers on 4-inch silicon-on-insulator wafers. A low-cost custom-designed digital holographic microscope (DHM) is employed to simultaneously monitor the thin film thickness, the surface topography and the curvature of each of the cantilevers before and after deposition. The variation in stress state across the thin film materials library is then calculated by Stoneys equation based on the obtained radii of curvature of the cantilevers and film thicknesses. DHM with nanometer-scale out-of-plane resolution allows stress measurements in a wide range, at least from several MPa to several GPa. By using an automatic x-y translation stage, the local stresses within a 4-inch materials library are mapped with high accuracy within 10 min. The speed of measurement is greatly improved compared with the prior laser scanning approach that needs more than an hour of measuring time. A high-throughput stress measurement of an as-deposited Fe-Pd-W materials library was evaluated for demonstration. The fast characterization method is expected to accelerate the development of (functional) thin films, e.g., (magnetic) shape memory materials, whose functionality is greatly stress dependent.

The Bain library: A Cu-Au buffer template for a continuous variation of lattice parameters in epitaxial films

Smallest variations of the lattice parameter result in significant changes in material properties. Whereas in bulk, lattice parameters can only be changed by composition or temperature, coherent epitaxial growth of thin films on single crystals allows adjusting the lattice parameters independently. Up to now only discrete values were accessible by using different buffer or substrate materials. We realize a lateral variation of in-plane lattice parameters using combinatorial film deposition of epitaxial Cu-Au on a 4-in. Si wafer. This template gives the possibility to adjust the in-plane lattice parameter over a wide range from 0.365 nm up to 0.382 nm.

Combinatorial Development of Fe–Co–Nb Thin Film Magnetic Nanocomposites

A Fe-Co-Nb thin film materials library was deposited by combinatorial magnetron sputtering and investigated by high-throughput methods to identify new noncubic ferromagnetic phases, indicating that combinatorial experimentation is an efficient method to discover new ferromagnetic phases adequate for permanent magnet applications. Structural analysis indicated the formation of a new magnetic ternary compound (Fe,Co)3Nb with a hexagonal crystal structure (C36) embedded in an FeCo-based matrix. This nanocomposite exhibits characteristics of a two-phase ferromagnetic system, the so-called hard-soft nanocomposites, indicating that the new phase (Fe,Co)3Nb is ferromagnetic. Magnetic hysteresis loops at various angles revealed that the magnetization reversal process is governed by a domain wall pinning mechanism.

Synthesis of Au microwires by selective oxidation of Au–W thin-film composition spreads

Abstract We report on the stress-induced growth of Au microwires out of a surrounding Au–W matrix by selective oxidation, in view of a possible application as ‘micro-Velcro’. The Au wires are extruded due to the high compressive stress in the tungsten oxide formed by oxidation of elemental W. The samples were fabricated as a thin-film materials library using combinatorial sputter deposition followed by thermal oxidation. Sizes and shapes of the Au microwires were investigated as a function of the W to Au ratio. The coherence length and stress state of the Au microwires were related to their shape and plastic deformation. Depending on the composition of the Au–W precursor, the oxidized samples showed regions with differently shaped Au microwires. The Au48W52 composition yielded wires with the maximum length to diameter ratio due to the high compressive stress in the tungsten oxide matrix. The values of wire length (35 μm) and diameter (2 μm) achieved at the Au48W52 composition are suitable for micro-Velcro applications.

Microgradient-heaters as tools for high-throughput experimentation.

A microgradient-heater (MGH) was developed, and its feasibility as a tool for high-throughput materials science experimentation was tested. The MGH is derived from microhot plate (MHP) systems and allows combinatorial thermal processing on the micronano scale. The temperature gradient is adjustable by the substrate material. For an Au-coated MGH membrane a temperature drop from 605 to 100 °C was measured over a distance of 965 μm, resulting in an average temperature change of 0.52 K/μm. As a proof of principle, we demonstrate the feasibility of MGHs on the example of a chemical vapor deposition (CVD) process. The achieved results show discontinuous changes in surface morphology within a continuous TiO2 film. Furthermore the MGH can be used to get insights into the energetic relations of film growth processes, giving it the potential for microcalorimetry measurements.